Note: Descriptions are shown in the official language in which they were submitted.
- 2 -
~31E~7B9
The invention relates to a process for the catalytic
hydrodesulphurization without catalyst replenishment
of vanadium- and nickel-containing residual hydrocarbon
oils. Processes of this type have been described in
our Canadii~ patent application 154836. ~-
The catalysts according to these patent applications
show a lifetime and average activity above a certain ;
fixed minimum, when applied for residue hydrodesulphurization
.j , , ~
, in a standard catalyst screening test. They have a total ~ ~
;
pore volume above 0.30 ml/g, less than 10% of the total
pore volume is present in pores with a diameter above
100 nm, and they have such a specific average pore diameter
(p) and specific average particle diameter (d) that
the quotient p/(d)-9 meets the requirement -
3 x 10 x (PH ) < p/(d) 9 < 17 x 10 x (PH )
in~which PH is the hydrogen partial pressure applied
(p in nm, d in mm, PH in bar). As is shown in the
I - patent application, catalysts having a quotient p/(d) 9 ;~
that is smaller than 3xlO 4x (PH )2 or larger than 17 ~-
;70 x 10 4 x (p~ )2 show a lifetime which is too short and/or
an average activity which is too low, in the standard
catalyst screening test, to meet the minimum lifetime
and average activity requirements laid down in the patent
'' ~ spplicatlon.
Continued research by the Applicant in the field
of residue hydrodesulphurization has revealed that operation
:,
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of the process in the presence of an amount of water correspond~
ing to a water vapour partial pressure in the process of 0.5-30
bar enhances the suitability of the catalyst for residue hydro~
desulphurization to a degree depending on the quotient p/(d)0 9
of the catalyst. In view of the beneficial effect which the pre- ,' ,,
sence of steam has on the performance of residue hydrodesulphur~
; ization catalysts, the minimum requirements for a good catalyst ~ J
in the above-mentioned standard catalyst screening test can be
considerably tightened, if this test is carried out in the presence ' -~
of steam. "~
It has now been found that o~ the catalysts according ',; ~ ,
j to the above-mentioned Canadian,patent application only those
`, having a quotient p/~d) which meets the requirement ~ ',,
4 x 10 4 x (PH l ~ p/(d~ < 17 x 10 x (PHz)
, ~ show a sufficien~ly long lifetime and a sufficiently high average
~, activity to meet the ~ightened requirements of the standard catalyst
" screening test in the presence of steam. Catalysts having a quo- ,
tient p/(d) 9 which meets the requirement ;
' 3 x 10 4 x (P~ p/(d) 9 ~ 4 x 10 x (PH2) ,
', 20 which catalysts conformed to the old requirements of the test
in thc absence of steam, fail to comply with the tightened require-
i ments of the test in the presence of steam.
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~3~71~
It has further been found that catalysts havingr
a quotient p/(d) 9 which meets the require~ent
17 x 10 x (P~ p/(d) 9 < 5 ~ 24 x lO x (PH )
which catalysts ~ailed to conform to the o.ld requirements
of the test in the absence o~ steam, conform not only
to these old requireme.nts in the presence of steam but
even to the tightened requirements in the presence of
steam. . ~ :
- The present patent application therefore relates
to a process for the catalytic hydrodesulphurization
without catalyst replenishment of vanadium- and nickel-containing
. residual hydrocarbon oils, which process is carried
out in the presence of an amount o~ water corresponding - ~ -
. ,, ~ .
.: - to a water-vapour partial pressure in the process of
0.5-30 bar and in the presence of a catalyst which has
~ a tota~ pore volume above 0.30 ml/g,less than 10% of
? .the total pore volume being present in pores with a diameter
- above lO0 nm, and such a specific average pore diamete.r
: ( p) and speci~ic average particle di.ameter (d) that
~0 the qUotient p/(d)'9 meets the requ;rement
4 x 10 I x (PH ) < p/~d) '9 ~ 5 ~ 24 x lO x ~PH )
in whi.ch PH is the hydrogen partial pressure applied
(p in nm, d in mm, PH in bar)
~or the way in which p and d are determined, reference
i9 made to our Canadian patent appl.iCation 154836 wherein the deternLina-
~ion of these parameters has been described extensi~ely.
" .
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~3~7~
According to the present invention the hydrodesulphurization
is carried out in the presence of an amount of water
corresponding to a water-vapour partial pressure in
the process o~ 0.5-30 bar. The amount of water applied
preferably corresponds to a water-vapour partial pressure
in the process of 1-15 bar and in particular of 1-5
,
` bar. The required amount of water may be added to the
gas and/or liquid stream which is passed over the catalyst.
Thè water may be added either as such or in the form
of steam. Water as such may, for instance, be added ;l ~
to the residual hydrocarbon oil to be hydrodesulphurized - -
or steam may be added to the hydrogen stream which is
supplied to the process. If desired, a water precursor
such as a lower alcohol, from which water is f~rmed
;.,
under the prevailing reaction conditions, may be added ~-
;~ instead of water.
The catalysts which are applied in the process
~ according to the inventlon preferably have~a total pore
;l~ volume above 0.45 ml/g and a surface area above 50 m~/g `~-
and more in particular a surface area above 100 m2/g.
It is ~urther pre~erred that the catalysts have such
a p and d that the quotient p/(d)-9 meets the requirement
4 x 10 4 x ~PH ?2 c p/(d) 9 < 4 ~ 13 x 10 x (PH ) ~ ?
The hydrodesulphurizakion according to the invention
, . . .
ic most pre~erably carried out in the presence o~ a catalyst
which has such a p and d that the quotient p/(d)0 9
meet~ thc requirement
~ ' '
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~L~3~89
-4 (p )2 c p/(d) 9< 4 ~ 13 x 10 x (PH2) '
and which catalyst has moreover a total pore volume
above 0.45 ml/g, with at least 0.4 ml/g of the total
pore volume in pores with a diameter of at least 0.7
x p and at most 1.7 x p, and a sharp pore diameter distribution,
characterized in that
(a) less than 20% of khe total pore volume is present
in pores with a diameter smaller than 0.7 x
p, and
(b) less than 20% of the total pore volume is present
in pores with a diameter larger than 1.7 x p.
If the latter catalysts are applied for residue
hydrodesulphurization according to the invention, they
show an excellent performance.
The catalysts according to the invention preferably
.
comprise 0.5-20 pbw and in particular 0.5~10 pbw nickel~
and/or cobalt and 2.5-60 pbw and in particular 2.5-30
pbw molybdenum and/or tungsten per 100 pbw carrier. The
atom1c ratio of nickel and/or cobalt on the one hand ~ -
to molybdenum and/or tungsten on the other hand may
vary widely, but is pre~erably between 0.1 and 5. Examples
o~ very suitable metal combinations for the present
catalysts are nickel/tungsten, nickel/molybdenumj cobalt/molybdenum
and nickel/cobalt/molybdenum. The metals may be present
on the carrier in the metallic form or in the form of
their oxides or sulphides. Preference is given to catalysts
s
according 'co the invention in which the metals are present
,, .
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3~378
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on the carriers in the form of their sulphides. In addition
to the above-mentioned catalytically actlve metalsg
the catalysts may contain other catalytically active
metals and promoters such as phosphorus, boron and halogens,
such as fluorine and chlorine. Very suitable carriers
. - , . ..
for the present catalyts are oxides of elements of Group
II, III or IV of the Periodlc Table of Elements such
as silica, alumina~ magnesia and zirconia, or mixtures ;
. ~ ,
of the said oxides such as silica-alumina, silica-magnesia,
alumina-magnesia and silica~zirconia, Preferred carriers
for the catalysts applied according to the invention
are aluminas and silica-aluminas.
The catalysts according to the inventlon may be
prepared by depositing the metals concerned on a carrier
which has such a specific average pore~diaméter that
:,,,; ~ --
after deposition a catalyst is obtained which meets the ` -; ;
requirements of the invention, either as such or after `
:- ..
l ~ the specific average particle diamet;er has been increased ~
I, .
or decreased. ~he catalysts according to the invention
are preferably prepared by single or~multistep co-impregnation
; of a carrier with an aqueous solution comprising one
or~more nickeI and/or cobalt compounds and one or more
.
molybdenum and/or tungsten compounds, followed by drying ~ -
~ :.
and calcining,
~ For information concerning methods which may be
employed to influence the porosity of the carrier material
or the catalyst and further details about preferred
. .
:'
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~1)3~7~3
rcutes to prepare the pres~n~ Cataly~ts, referenCe i9 made :-
to our Canadian patent application 154,836, in which thes~
subjects have been discussed extensively.
The catalytic hydrodesulphurization of residual
hydrocarbon oils without catalyst replenishment i5 preferably
e~fected by passin~ the hydrocarbon oil at elevated
temperature and pressure and,in the presence of hydrogen
and steam in upward, downward or radial direction through ,
one or more verticaliy disposed fixed catalysts beds.
The hydrodesulphurization may be carried out either
in a single reactor or in two or more reactors. As
a rule hydrodesulphurization reactors contain more than
one catalyst bed. The catalysts applied in the separate
catalyst beds and/or in the separate reactors may differ
from each other with respect to their p and/or d and/or
chemical composition. If in the hydrodesulphurization '
according to the present invention separate catalyst
beds and/or separate reactors are used, it may be attractive
to introduce s~eam into the process by the addition of
water between two or more Or the catalyst beds or reactors.
In this way the addition of water helps to lower the
temperature of the partly hydrodesulphurized product
which has risen as a result of the exothermic hydrodesulphurizatio~
reaction.
The specific average particle diameter of the catalysts
applied accordin~ to the invention is as a rule 0.5-2.5 mm
-` - 9 - ~:~
~lg78~
and preferably 0.6-2.0 mm. I~ the value of d which `
according to the invention is required to obtain a good
catalyst performance at a glven p and PH is too small
for practical application, the hydrodesulphurization
may be carried out in the presence of porous agglomerates
which have been prepared from the small catalyst particles
in the way described in our ~anadian patent application
.,
154,836
The hydrodesulphurization process according to ;
10 the invention may be operated under widely varying conditions.
The hydrodesulphurization is preferably carried out
at a temperature of 300-475C, a hydrogen partial preesure
of 30-200 bar, a space velocity of 0.1-10 pbw of fresh
feed per pbv of catalyst per hour and a hydrogen/feed
~ ~ 15 ratio of 150 2000 Nl H2/kg feed, Particularly preferred -
i ~ ~ conditions are a temperature of 350-445C, a hydrogen i ;~
i partial pressure of 40-160 bar, a space velocity of
j~ ~ 0.3-3 pbw of fresh feed per pbv of catalyst per hour ~ -
and a hydrogen/feed ratio of 250-1000 Nl H2/kg feed. ;
The hydrodesulphurization process according to
the present invention may very suitably be preceded I `
by a demetallization process, in order to diminish the
deactivation of the hydrodesulphurization catalyst.
This demetallization is preferably conducted in the
presencè of hydrogen and a catalyst.
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- 10 - ,
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~387~ :
An investigation by the applicant into the effect
of catalytic hydrodemetallization Or residual hydrocarbon
oils on the lif`etime Or catalysts which are employed
accordin~ to the present patent application for the
hydrodesulphurization of the demetallized oils in the
presence of steam has brought to light some surprising
facts, which can sui~ably be elucidated with the aid
of the following general considerakion which is based
on experimental data.
If three vanadium- and nickel-containing residual
hydrocarbon oils (oils 1~ 2, 3) obtained by distillation
a~d having metal contents M~, M2 and M3, respectively
(Ml~M2<M3), are subjected to a hydrodesulphurization
-under identical conditions with regard to catalyst,
pressure, amount of water, maximum temperature~ space
velocity and gas throughput rateS according to a process
as described in the present patent application, the
~ catalyst employed shows li~etimes of Ll, L2 and L3,
t respectively (Ll>L2>L3j. It turns out; that in each case
the product of L and M is virtually constant (LlxMl-L2xM2=L3xM3)
or, in other words, the lifetime of the catalyst and
the metal content of the feed are virtually inversely
proportional. Catalytic hydrodemetallization of the oils
2 and 3 offers a possibility of hydrodesulphurization
o~ these feeds as well with the same catalyst such that
s the lifetime Ll is attained. The question here is,
however, to whet level the demetallization has to be
,~
. ,
~3 !37~ ;
pursued. In view of the above-mentioned inverse proportionality
one mi~ht expect that demetalllzation of the oils 2
and 3 to a metal content Ml would bring about the desired
extension of catalyst lifetime. In point of fact, however~ ~;
demétallization of oil 2 to a metal content Ml (per
cent by weight of metal removed
M -M
V2 ~ ~ x 100) and deme~;allization of oil 3 to a
metal content
Ml (per cent by weight o~ metal removed
V3 ~ ~ x 100) lead to lifetimes of the desulphurization
catalyst of L2' and L3', respectively (L3~>L2~L
- Evidently, the inverse proportionality between catalyst~
lifetime and metal content of the feed noted above for ~ - -
the desulphurization of residues obtained by distillation
does not hold good;for the desulphuri&ation of such
residues after partial demetallization. For oil 2 a
demetallization to a metal content M2'(M2'>Ml)-suffices .
to extend the lifetime of the desulphurization catalyst '!
from L2 to Ll. In view of the aforesaid one might expect
that a demetallization of oil 3 again to a metal content
M2~ would also extend the lifetime of the desulphurization
catalyst for this feed to Ll. In actual fact, however,
deme~allization of oil 3 to a metal content M2~ leads
to a lifetime L3~ of the desulphurization catalyst (L3"~L
Evidently~ tbe demetellisation is still too deep. For
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--~. l2 -
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oil 3 a demetallization to a mekal content M3'(M3'~M2')
su~fices to exte~d the lifetime of the catalyst ~rom
L3 t.o Ll.
In view of the foregoing consideration the following
conclusions can be drawn with regard to the catalytic
hydrodemetallization of' residual hydrocarbon oi.ls as
a means of extending the lifetime of the catalyst employed
in a process according to the present patent application
for the hydrodesulphurization of the demetallized oil.
In order to increase the lifetime of these catalysts
to a certain fixed level it is concluded: :~
l, that a demetallization which is far less deep
than one would expect on the basis of an as6umed -~
inverse proportionality between the metal content
-~ ~ 15 of the feed and the lifetime of the catalyst
suffices (M2 >Ml;M3 >M~
1 2. that according as the feed has a higher metal
fi content, a larger quantity of the metals should ~ :
be removed (M3-M3 ~M2 M2 )'
3. that according as the feed has a higher metal
content, a less deep demetallization suffices
(M3 >M2 )' ' -
' A~ter continued research on this subject the Applicant
has succeeded in quantifying the a~oresaid qualitative
conclu~ions and formulaking a relation between the metal
content of a re~idual hydrocarbon oil before and a~ter
catalytic hydrodemetallization and the lifetime Or
~ ~,
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.~ - 13 -
1~3~7~g , ~
catalysts employed in a process according to the present .
patent application for the hydrodesulphurization o~
the residual hydrocarbon oil before and after demetallization.
In the ~ormulation o~ this relation the following restrictions
ha~e been taken into account: :
1 The metal co~tent of the hydrocarbon oil before
demetallization (Ml) may vary between 25 and
1500 pp~lW. .
2. The lifetime o~ the desulphurization catalyst ~
10 . employed for the demetallized oil (L2) may vary ~ :
between 2doo and 16000 hours
3. The quotient of the metal contents of the hydrocarbon :
oil after and before the demetallization (M2 - -
and Ml~ respectively) may vary between 0.75 and
0.10. ~ :
4c The product of the metal content of the hydrocarbon .
oil before demetallization (Ml) and the:lifetime
of the desulphurization cataIyst employed for ~
the demetallized oil (L2) may vary between 2x105
and 3xlO .
Taking into account the a~oresaid restrictions
1~4, the relation reads as follows~
M2 =(1.05 + 0.20) x Ml x (Ll/L2)0'5,
where M~ and M2 represent the metal content of the hydrocarbon .: .
oil before and after demetallization, respectively, and
. ~ . . .
: Ll and L2 the lifetimes of the desulphurization catalyst
whcr. employed ~or the non-demetalli~ed and the demetal:ized ~ ;
.
,
"
~ 14 -
~8~8~ ::
oil, respectively. This relation o~ers the possibility
of establishing to what level the metal content of a
residual hydrocarbon oil used as feedstock for the process
according to the present patent application should be
lowered in order to extend the life of the desulphurization
catalyst by a specific number of hours.
The demetallization of residual hydrocarbon oils
is pre~erably carried out by passing the hydrocarbon
oil at elevated temperature and pressure and in the presence
of hydrogen in upward, downward or radial direction -
through one or more vertically disposed reactors comprising ~
a fixed or moving bed of suitable catalyst parkicles. ,
A very attractive embodiment of the demetallization ~ ;
process is one in which the hydrocarbon oil is passed
through a vertically disposed catalyst bed in which
; during operation fresh catalyst is periodically introduced
at the top of the catalyst bed and spent catalyst is ~ ~;
withdrawn at the bottom thereof (demetallization in
bunker-flow operation).
Another very attractive embodiment of the demetallization
procesæ is one in which several reactors comprising
a fixed catalyst bed are present, which are alternately
used ~or demetallization. While the demetallization
i8 carried out j.n one or more of these reactors, the :~
catalyst is replenished in the other reactors (demetallization
ln ~ixed-bed swing operation) If desired, the demetallization
may also be carried out by ~uspending the catalyst in ;~
'~' ,
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1;he hydrocarbon o:il to be demetallized (demetallization
in slurry-phase operation).
If the hydrodesulphurization according to the invention
is preceded by a demetalliæation, it may be attractive
to introduce steam in the process by the addition of
water to the demetallized product a~ter its lqaving
the demetallization reactor and before its entering ~ '
- the first hydrodesulphurization reactor. In this way ''
the addition of water helps to lower the temperature
o~ the demetallized product which has increased as a `'~ '
result of the exothermic demetallization reaction. Suitable
catalysts for demetallization of residual hydrocarbon
oils are catalysts comprisin~ one or more metals with - '
hydrogenation activity on a carrier.
If the desulphurization according to the invention ' ;''~'~
,...
'is preceded by a demetallization, the demetallization '
i's preferably carried~out in a bunker-flow operation
or in fixed~bed swing operation and'the desulphurization
in conventional fixed-bed operation.
Examples o~ feeds that may be subjected to the hydrodesulphuri-,'' ~'''
za~ion process accordlng to the invention (whether '' ' ~;
or not pre¢eded by a demetallization process) are crude
oils and residues obtained by distilling crude oils
at atmospheric or reduced pressure. Residues obtained ~ ~ '
by distilling the products originating ~rom the thermal
or catalytic cracking of heavy hydrocarbon oils may
al~o be hydrodesulphuri~ed accordlne to the invention.
.
, ,"
- 16 -
~3~7~
The invenkion will now be elucidated with the following
examples.
EXAMPLE I
__
The influence of steam on the performance Or catalysts
for the hydrodesulphurization without catalyst replenishment
of vanadium- and nickel-containing residual hydrocarbon
oils was determined for twelve catalysts and three residual
oils with the aid of a standard catalyst screening test.
In this test the oil together with hydrogen was passed -~
downwards through a vertically disposed cylindrioal
fixed catalyst bed at a temperature of 420~C, a hydrogen
, . . .
partial pressure varying from 40 to 200 bar, a water-~apour ~
partial pressure varying from 0 to 30 bar (obtained .- :-
by adding varying amo~nts of water to the oil), an exit ~ ~
: 15 gas rate of 250 Nl/kg:of fresh feed:and a space velocity : :
o~ 4.35 kg of oil per kg~of catalyst per hour. The compositions
: and properties of the catalysts, which were applied :
in the form of their sulphides, are given in Table I. ~:
For~ information concerning the preparation of the twelve ;
catalysts used in the present experiments, reference :
- is made to the working examples o~ our C~adian -
patent application 154,836 , in which the preparation
of these catalysts has been described extensively.
. ' , '.
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L~ ~ h r-l ~ I o o o o o o o o o o o t ~ :
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¦ ~ t ~ ~ ¦ ~
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L~ I t ~ t ~ oo ~ I ~-
.~ htc7 t ~ ~r ~ t~ I l ~ l l l l l l ;
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The three residual oils used in the present experiments
may be described as follo~s.
FEED I: ~-
~ , .
Oil having a total vanadium and nickel content of 462 .
ppmw, a C5-asphaltenes content of 15.4 %w and a sulphur
content of 2.7 %w, which oil had been obtained as a
residue in the distillation under reduced pressure .;
of an atmospheric distillation residue of a Caribbean .
crude oil. t . ', :
FEED II:
Oil having a total vanadium and nickel content o~ 62
ppmw, a C5-asphaltenes content of 6.4 %w and a sulphur
content of 3.9 %w, which oil had been obtained as a
: residue in the atmospheric distillation of a Middle-East .
-, ,
crude oil.
: FEED~
Oil having a total vanadium and nickel content of 245
ppmw, a C5-asphaltene scontent of 7.2 %w and a sulphur
.~ - content of 2.1 %w, which oil had been obtained as a
residue in the atmospheric distillat-Lon of a Caribbean , ~ ;
crude oil. . ,;
The performan.ce of a catalyst for the hydrodesulphurization . ~ :
without catalyst replenishment of vanadium- and nickel-containing
residual hydrocarbon oils may be described with the
aid of the catalyst li~e and the average activity (kaVerage), ~ .
whi¢h are de~ined as follows: ~
,. ' :
,, ;. .
~, .
~, ,' . .
-- 19 :
~ 3 87
The catalyst life (expressed in kg feed/kg catalyst)
is the maximurn amoullt Or residual oil that can be hydrodesulphurized
over the catalyst before a rapid deactivation sets in.
The average activity (expressed in kg feed/kg catalyst.hour
(%w S~) is the activity of the catalyst at the hal~-way
point in the catalyst life.
The minimum lifeti.me and average activity requirements
which a catalyst should meet in the standard catalyst
screening test in the presence of steam, with each of ..
the.three feeds, in order .to rate as a good or excellent ~ ;
catalyst according to the present invention, are collected
in Table II. For comparison, the minimum lifetime and ;.
average activity requirements which a catalyst should
meet in the standard catalyst screening test in the absence `.-. .;
: 15 . f steam,.with each of these feeds, in order to rate ` ~;
.
as a good or excellent cata.lystg have also been incorporated ;:
in table II. The minimum requirements for a good or
excellent catalyst for the hydrodesulphurization of .~:
Feeds II and III in the absence Or steam are the same
as those already laid down in our Can~dian pat~nt appliCation~ .
..
154,836 and 177,438.
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o
o I o
I ~ I IAl I Al
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ILn I o I :
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The results of the hydrodesulphurization experiments ..
are given in Tabel III.
TABLE III
No. No. No. 2 2 litfaélYkg feed/ .~-
barbar kg ~eed/kg kg cat.
cat hour ,~
,~,%w S~
1 A I 130 20 1.8 2900
2 A I 130 2 1.8 2800
3 A I 130 10 1.9 2800
4 A I 108 7 1.6 3100
-
B II 125 5 306 > 15000
6 I II 65 15 2 >4
7 A III 125 5 4 2 ~3000
8 A III 70 10 2.1 ~ 5700
9 M II 85 5 ~1.8 > ~10000
C III ~70 3 l.9 ~~10000
F II:~150 20~ ~10.0 ~2700
12 H II 150 10 6.o~: 3250
13 ~ II 50 10 1.2 ~ 12000
14. Z II 150 30 ~ 0.75 4000
D III 200 10 13.0 700
16 ~' III 150 15 ~ 5. 1500
17 A III 40 2 1.7 ` 1500
18 Y III 100 15 2.5 1500
19 A I 130 - 1.15 2200
A I 115 - 0.95 2800
21
"~;` (
~ 22 - ~
B789
TABLE III (cont'd)
No. No. No. H2~ H20~ kaverage' cataIyst
bar bar kg feed/kg kg cat~
cat.hour.
-- ( ~ 2
21 A I 15C - 1.4 1600 `
; 22 F II 150 _ 7.2 2800 ~ -
23 H II 150 - 4.1 3100
24 B II 125 ~ 2.1 > 15000 ; ~
I II 65 - 1,2 >4000 - ;
26 M II 80 - 0,7 ~ 10000
27 0 II 5O - o.6 ~ 12000 .
; 28 Z II 150 - 0,5 >4000
29 D III 200 - 12.0 660
T III 150 - 3:.3 1600
~ 31 A III 125 _ 2.5 ~36~oo ^ : -
;32 ~ A III~ 70 - :o.g : 6000 .
33 C III ~,:70 - ~ o.7 9800 :~
34 A III 40 _ 1.5 1400
Y III 100 ~ 1.3 l40b
~ The experiments 1-10 conducted in the presence o~ steam were /-: ~
,-j , . ..
hydrodesulphurization experiments according to the
~; presçnt invention.
In the experiments 1-8 catalysts were applied
which had a "cotal pore volume above 0.45 ml]g with more
:,~,
than o.40 ml/g of the total pore volume in pores wlth
a diameter of at least 0.7xp and at most 1.7xp, a "sharp
, .... .. .
, ''`' ~'~ ~.
~.
,
,,
... . ..
~ 23 ~
3~3~7~9 ~:
pore~diameter distribution" as defined and a quotient
p/(d)'9 which met the requirement
4 -4 (p )2 ~ p/(d) 9 < ll ~ 13 x 10 x (P~2) .
The perrormance of these catalysts was excellent. In
the experiments 1-4 with Feed I the catalyst had a life i~
average >1Ø In the experiments 5 and i
6 with Feed II the catalysts had a life >4000 and a
kaVerage >2,0. In the experiments 7 and 8 with Feed
III the catalyst had a life >2500 and a kaVerage >Z~~
The experiments g and 10 were carried out with ~ ;;
the aid of catalysts having a quotient p/(d)'9 which
l~ met the requirement
`~ 4 0-4 (p )2 < p/(d)'9 < 5 ~ 24 x 10 x (
The performance of these catalysts was good, In experiment
9 with Feed II the catalyst had a life >3500 and~a kaVerage
>1.5. In experiment 10 with Feed III the catalyst had~
a life ~2500~and a kaverage 5 , ~
The experiments 11-18 conducted;in the presence ~ -
- of steam were hydrodesulphurization experiments which
fall outside the scope of the present invention. They
; ~ have been included ror comparative purposes.
The experiments 11 and 12 were carried out with
the aid of catalysts having a quotient p/(d)'9<4xlO 4x(PH ?2. :~
In these two experiments with Feed II the catalysts
had a life <3500, ~-
In experiment 13 a catalyst was applied which had
a quotient p/(d)'9~5~24xlO 4x(P~l )2 and in experiment
.. . . .
' '
',
"'
'"
,.
- 24 -
8~
14 a catalyst which had more than 10~ of the total pore
volume in pores with a diameter above 100 nm. In these
two experiments with Feed II the catalysts had a kaVerage
~1.5.
The experiments 15 and i6 were carried out with
catalysts having a quotient p/(d)'9<4xlO ~x(PH )
experiment 17 with a catalyst having a quotient p/(d) 9~5~24xlO 4
(PH )2 and experiment 18 with a catalyst havihg more
than 10% of the total pore volume in pores with a dîameter ;
above 100 nm. In these four experiments with Feed III ,
the catalyst had a life <2500.
The experiments 19-35 conducted in the absence ,
of steam were hydrodesulphurization experiments falling
outside the scope of the present invention. They have ~ ~
been included for comparative purposes. ~ ;
The beneficial influence of the presence Or steam , ~ -
on the performance of the catalyst appears clearly from ~ `
- :.., :
a comparison of the results obtained in the experiments
listed side by side in Table IV.
`".'''' '':.''
": ,. . .
;~, ', ,
"'
''; , :, ,:
.
,
, .
:~,., , . , , ~
,~ - ,
, - 25
~L~387~
'Table IV ..
No. o~ exp. in No. of comparati~e Feed No. Cat.No. PH ,bar
in the presence in khe absence of 2 ,:
o~ steam Or steam.
_______________ ____________~_____ _____ __ _______ __~__ . ,
.
1,2,3 ' 19 I A 130 ,, ;, , ,
11 22 II F 150
12 23 . II H 150 .' .
24 II B 125 "
6 25. II I 65 ;. ;,~
9 ' '26 II M 80
-13 27 II 0 ..50
14 28 II Z 150
: 15 29 III D 200 ~ :
16 30 III ' T ~ 150 ,~
~ , , 7 31 III A ' 125
`~ : 8 . 32 III A 70
,10 33' III C 70 ,
17 ,34 III A 40 "~
, 18 35 III Y 100 '~
======_==e___=_=====~==~======_===~~=~=~=====_===_ =__==__=== ~ ~ .:
,~ . The comparative experiments 19 and 20 with Feed ,
~,~ I and 31 with Feed III were hydrodesulphurization-
,; , experiments falling within the scope of our Canadian
patent applioation 177,438, In these experiments, carried
', 5 out in the absence o~ steam, the oatalysts showed
' an excellent per~ormance. ,' -
' The ,comparative experiment 21 with Feed I
wes a hydrodo~ulphuri~etion oxporiment
'' ' ' ' ' ' -
, ~ - .
89 ~ ~ -
falling within the scope of our Canadian patent application
177,988. In these experiments~ carried out in the absence
of steam, the catalysts showed a good performance. -~
The comparative experiments 23 and 24 with Feed
II were hydrodesulphurization experiments falling within
the scope of our Canadian patent application 154,8360 In
these experirnents, carried out in the absence of steam the
catalystsl performance was good and excellent, respectively. -
The comparative experiments 22, 25, 26 and 27 with
Feed II and 29, 32, 33 and 34 with Feed III were conducted
in the presence of catalysts having a quotient p/(d)0-9 which
failed to meet the requirement
3 x 10 x (PH ) ~ p/~d) < 17 x 10 ( H2) ; ~ ;
In these experiments, carried out in the absence of steam~
the catalysts showed an insufficient performance. `~
In the comparative experiments 28 with Feed II and
35 with Feed III catalysts were applied which had more than
10% of thb~total pore volume in pores with a diameter above
.. ~. :.
100 nm. In these experiments, again carried out in the
absenca of steam, the catalysts showed an insufficient per- ~-
formance.
AMPLE II -~
Four vanadium- and nickel-containing residual hydro-
carbon oil~ (oils IV-VII) were desulphurized with or without
preceding demetallization. The deswlphurization ~dfIthe
.
- 26 -
.~,,,, :
- 27 -
~ 3 ~
oils was effected by passing the~ at elevated temperature
and pressure and in the presence of hydro~en and steam
in downward directi.on through a vertically disposed ^~
Pixed bed of desulphurization catalyst A.
The demetallization of the oils was effected by
passin~ them at elevated temperature and pressure and
in the presence of hydrogen in downward direotion through
a vertically disposed fixed bed of a demetallization `~
catalyst. The demetallization catalyst contained 0.5
pbw nickel and 2.0 pbw vanadium per 100 pbw silica carrier. -~ ;
The f`our residual oils used in the present experiments ;~ -
may be~described as follows. ,
FEED IV~
Oil havlng a total vanadium and nickel content
of 200 ppmw and a sulphur content of 2.0 %w, whlch oil
had been obtained as a residue in the atmospheric distillation
of a Caribbean crude oil.
FEED V~
Oil having a total;vanadium and nickel content
~; 20 of 393 ppmw and a sulphur content of 2.8 %w, which oil i~ ,
had been ontained as a residue in the atmospheric distillation
~ , ~
of a Caribbean crude oil.
FEED ~
Oil ha~ing a total vanadium and nickel content of
51 ppmw and a aulphur content of 4.0 %w, which oil had ~
been obtained aa a reaidue in the atmospheric distillation
o~ e Middle-Ea~t oruùe oil.
,, .
, ,,~
,,
' ,"'
~ 28 - ';
FEED VIl: 1~38789 ; ~ ~
~ .,
Oil having a total vanadium and nickel content '', '
of 100 ppmw and a sulphur content of 5.3 %w, which oil
had been obtained as a residue in the distill~tion under,
reduced pressure o~ an atmospheric distillation residue ,
of a Middle-East crude oil.
In each of the experiments described hereinafter :,, ,
one of the Feeds IV - VII was desulphurized under speclfic ,.-~
~ conditions to~a certain sulphur content (experiments ' -:,
: 10 36-40), whereupon that same oil was first partially ',~
demetallized and subsequently desulphurized under the .'~'' ;~ ,
same conditions and to the same sulphur content (experiments '; ; :
41-45). The starting temperature of the desulphurization ,,' ~ '
experiments was choosen as low as possible, such that
~;~15' under the~given reaction conditions a product havlng '~
-~ , the,desired sulphur content could just be preparedO ''~ -'' .-
For the preparation of a product wlth a cons,tant sulphur .; ,~
content it was necessary to raise the temperature-gradually ,~ '",~
durin~ the experiments. The desulphurization experiments~
were dlscontinued at the moment the temperature had - .,~'
to be raised above 420C in order to prepare a product '.
'~ having the desired sulphur content.
The desulphurization condi~ions together with the ''-~
~: results of the experiments are collected in Table V. ' ~ ~ .
,, .
,~ , - .
:'
" ::
., ~ " : ,
. . .
, .. . .
,,, , ; . .
.
,_ 29 - .. : ~ .
~3~7~3g
Lm p o o Ln Ln o Ln ~ o o ~ '
-~t I H O Ln ~u
I ~u ~u o ~ o ~r Ln
I Ln
OI ~ O O L~ Ln o Ln r-- o o
~I H o ~Ln ~ O O
o ~ ~o 3 0
~ -,
JI H O 1~ 1~Ln Ln o o o o cc)
J l H o ~ ~D ~r ~1 o O Ln
I p ~1 Ln ~ Ln o
au H O t~ 1~ Ln Ln O O O O :'-
~1 H O ~O J ~1 o Ln
I p ~ Ln ~ Ln
- ~I H ~1 0 o o Ln ~ o o o J . ::
Ln ~ o
I J ~ Ln o
0 ~
o~ ~ o o o Ln C- o o o
r~l pLn ~ . w ~ ~ o o
J ~ I Ln J
Ln
L~
D 1~ ~1 O O . J
n
~-1 p ~ o~ o Ln Ln o o o o
~'~ P
~1l p O OLn Ln L~ Ln o o o o
~ . ~ ~ I H O Ln ~u
:~::,~ I ~J ('J O t" ~ ~I J O : ." "~
-': ~: I : :: .
DI ~ O O L~ Ln L~ Ln o o o
t~\l H O Ln (U O O
,~
,, ~, ,1~ -
h
h
,~ h ~~ rl o rd
n C~ h a~ N
o ~ h ~I H C) r3 ~rl ~1
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~1 ~ ~rl 1 U~ r~
~~ C) ~ Q~ QJ r~ ~ O H ,~ ~ (~
Yr1 t~ rl h h ~ o ~rl ~ Q,
" I~ ~d ~ ~ rl 120 ~rl~ ~ H
I, . r l O ~ O
~rl ~ h O ~d H h rdN ~3 U~ 0 ~
0 ~ O P- ~ h ~ h ~rl a~ ~ 0 4-1 ~ -
O C~ , O ~rl ~ ~ h ~ ~ ~ rl I~J ~
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q)S~rl ::1 N t~ Ul h 4~ ~ ~i X ~:
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~1 C c> v~ R- h ~ I bO ~ ~rl ;~ al Q) X
a) l O r1 ~ ~ O h al O r l ~ h
E3 1 ~ h ~ ,C h h a)c~ h ~ rl 11
~rll O :S aJ ~ ~ ~d 'd ~ ~ 5 0 (U ~ ~) U~ ~-
hl Z ~ h a) r~l ~ P~ h ~d ~rl aJ (`U
1U I ~d ~ rl ~ ~ C/~ ~L'2 ~11 5
Pl rl~7 r~ U) U~ ~ u~ O~
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A I V I ~ U~
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3 1 1 ::
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A I V I r~
o ~ 0:
:,c . :: : .
A 1~ V 1 3 ~
E a~ ~ i "~ ~ .
:: ~ : I ~ ~ Q. ~ P
.C .~:: .c p a) i .~
, ~ i' O ^ ~ ~ ~~ O.Ci ~ ~ ~ ,-,". ' ~ -
4~= o ~ o ~ ^
X
1: Il) ^rlN (L) ~I N ,~ ~ I
o ~ o o ~ r~ r-l `~= I ~ ~''
O ~rl N O h = h -d = t~l I .
r1 ~ O O ~ ,~ .~ ~ X
i ol ~ ~d U~~ N r~l ,~ O r-l O N
~i ~d ~1~ r~l a) ~l ~d a) O ~ 11
a rl ~ ~d ~ O ~ :
~l ~ hO ~O h ~ h
~rll~q vl ~3 0 h ~ O r1 ~ X
U r-l ~ O O ~rl O ~~I I :,
d ~d ~rl ~ O r~
, ~
, ,
-
, ,, .i ,
... .
31-
~he experiments 41-45 were experiments accordin~
to the present invention. In these3 the desulphuriæation ',
was preceded by a demetallization to a metal content ~
within the ran~e covered by the formula '; ,~,
(1.05 - 0.20) x Ml x (Ll/L2)0-5. Also, in these experiments
the other four requirements with regard to Ml, L2, M2/M
and Ml x L2 were satisfied. ,,~
The experiments 36-40 were also experiments,according
to the present invention. In these~ however, no preceding
demetallization was applied. For the calculation of ' ~,
M2 in the experiments 41-45 with the aid of the formula
M2 ~ (1.05 - 0.20) x Ml x (Ll/L2)0-5 use was made of
the values of Ll found in the experiments 36-40. - '~
~ It should be realized that the values of Ll, M2"
,
15 and 12~ stated in Table V were established in the desulphurization ,;~
and~demetallization experiments described hereinbefore
(in contrast with the values ment~ioned ~or M2, M2~ and , ,~
L2~, which were calculated, and for Ml and L2, which
were~given).
- ', ' . ;~
' ' ' , '. ':
~:
.~ : , , .'~ :
,
''
.,
'' ' ' ,
.
:: , , .
